Stabilized divalent germanium and tin compounds, processes for making the compounds, and processes using the compounds

ABSTRACT

Divalent germanium and tin compounds are provided. The divalent germanium and tin compounds have been found to be efficient catalysts for the formation of polyurethanes. Methods for making polyurethanes using the catalysts are also provided.

FIELD OF THE INVENTION

The present invention relates to novel divalent germanium and tincompounds that are stabilized by sterically bulky P^O ligands, processesfor producing the compounds, and polyurethane polymerization processesusing the compounds as catalysts.

BACKGROUND

Coating manufacturers have achieved significant progress in developingnovel components for polyurethanes to improve coating properties,although a need remains for novel catalyst systems. The usual catalystsfor forming polyurethanes are dibutyltindilaurate and tertiary amines.Dialkyl and trialkyltin derivatives, classes of the compounds to whichdibutyltindilaurate belongs, have been discussed as having some issuesregarding human toxicity. See, for example, Boyer, I. J., Toxicology,1989, 55, 253 and Lytle, T. F.; Manning, C. S.; Walker, W. W.; Lytle, J.S.; Page, D. S., Appl. Organomet. Chem., 2003, 17, 653. Divalent tincompounds as disclosed herein, which do not have alkyl-tin bonds, havenow been found to be suitable as catalysts for polyurethane formation.

Organometallics of the group 14 elements, particularly dibutyltinderivatives, are known to catalyze transesterification,transcarbamoylation and urethane formation. While there has beenprogress in development of novel components for polyurethanes to improvecoating properties, a need remains for novel catalyst systems. Typicalcatalysts for processes including transesterification,transcarbamolylation and urethane formation are dibutyltindilaurate andtertiary amines. Dialkyl and trialkyltin derivatives, classes of thecompounds to which dibutyltindilaurate belongs, have some toxicity tohumans; therefore, less toxic catalysts are desired.

Jousseaume, B. et al., (“Air Activated Organotin Catalysts for SiliconeCuring and Polyurethane Preparation” (1994) Organometallics 13:1034),and Bernard, J. M. et al. (U.S. Pat. No. 6,187,711) describe the use ofdistannanes as latent catalysts.

Co-owned and co-pending U.S. Pat. Applications (CL-3191, CL-3464 andCL-3193), all hereby incorporated by reference in their entirety,describe different classes of tin and germanium compounds useful ascatalysts. (CL-3191) describes divalent tin compounds stabilized byphenoxy groups with bulky ortho-substituents. (CL-3193) describesquadrivalent tin and germanium compounds containing more than onetriorganylsilyl groups connected to tin or germanium.

SUMMARY OF THE INVENTION

The present invention provides, in some embodiments, a compound havingformula:

wherein

E is tin (Sn) or germanium (Ge);

X is oxygen, sulfur, nitrogen, substituted N, or a lone pair ofelectrons;

n is 1 or 2;

R¹ and R² are each independently H, C-4 to C-50 alkyl, C-6 to C-50 aryl,silyl, C-4 to C-50 substituted arylalkyl, C-6 to C-50 substitutedalkylaryl, alkoxy, dialkylamino, or alkylhio; and

R³ and R⁴ are each independently C-1 to C-20 alkyl, or C-1 to C-20fluoroalkyl.

Further provided in some embodiments of the present invention is aprocess for making a divalent tin compound of the formula

wherein E is tin (Sn);

X is oxygen, sulfur, nitrogen, substituted N, or a lone pair ofelectrons;

n is 1 or 2;

R¹ and R² are each independently H, C-4 to C-50 alkyl, C-6 to C-50 aryl,silyl, C-4 to C-50 substituted arylalkyl, C-6 to C-50 substitutedalkylaryl, alkoxy, dialkylamino, or alkylhio; and

R³ and R⁴ are each independently C-1 to C-20 alkyl, or C-1 to C-20fluoroalkyl;

said process comprising:

-   -   providing a phosphine substituted with one or more sterically        hindered group, and a substituted tin II compound;    -   combining said phosphine and said tin(II) compound in the        presence of a solvent; and    -   isolating the resulting divalent tin compound.

Further provided in some of the embodiments of the present invention isa process for making a divalent germanium compound of the formula

wherein E is germanium (Ge);

X is oxygen, sulfur, nitrogen, substituted N, or a lone pair ofelectrons;

n is 1 or 2;

R¹ and R² are each independently H, C-4 to C-50 alkyl, C-6 to C-50 aryl,silyl, C-4 to C-50 substituted arylalkyl, C-6 to C-50 substitutedalkylaryl, alkoxy, dialkylamino, or alkylhio; and

R³ and R⁴ are each independently C-1 to C-20 alkyl, or C-1 to C-20fluoroalkyl;

said process comprising:

-   -   providing a phosphine substituted with one or more sterically        hindered group, and a substituted germanium 11 compound;    -   combining said phosphine and said germanium (II) compound in the        presence of a solvent; and    -   isolating the resulting divalent germanium compound.

Still further provided in some of the embodiments of the presentinvention are processes for producing polyurethanes by combiningisocyanate-comprising materials with isocyanate-reactive materials inthe presence of compounds of the present invention, used as catalysts.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an ORTEP drawing of tin(II),trans-bis[3-(di-tert-butylphosphino)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanolato-O,P]—.

FIG. 2 shows an ORTEP drawing of germanium(II),trans-bis[3-(di-tert-butylphosphino)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanolato-O,P]—.

DETAILS OF THE INVENTION

The present invention provides, in some embodiments, novel tin andgermanium compounds. The invention also provides, in other embodiments,processes for making the novel tin and germanium compounds, andpolymerization processes using the compounds. The new compounds do nothave direct alkyl bonds, which are usually associated withhigher-than-desired human toxicity, making them desirable candidates foruse as catalysts in polyurethane formation.

It has been discovered that a sterically bulky phosphine can be used asa starting material to form the aforesaid novel tin and germaniummaterials. The catalysts of the present invention comprise stericallyhindered groups. Sterically hindered groups are generally “bulky”, aswill be recognized herein by those skilled in the art, and as usedherein, the term refers to compounds having a spatial arrangement oftheir atoms such that most reactions with another molecule are preventedor retarded.

The compounds of the present invention are of the general formula

where E is tin (Sn) or germanium (Ge); X is oxygen (O), sulfur (S),nitrogen (N) or substituted N, or a lone pair of electrons; n is 1 or 2;R¹ and R² are each independently H, C-4 to C-50 alkyl, C-6 to C-50 aryl,silyl, C-4 to C-50 substituted arylalkyl, C-6 to C-50 substitutedalkylaryl, alkoxy, dialkylamino, or alkylthio; R³ and R⁴ are eachindependently C-1 to C-20 alkyl, or C-1 to C-20 fluoroalkyl.

Typically, R1, R1′, R2 and R2′ are tert-butyl or phenyl. When X issubstituted N, the substituents can be C-1 to C-10 alkyl and ═N—N═N-Ad,where Ad represents an adamantyl group:

When n is 2 in the formula above, the structure can appear as

where E is tin (Sn) or germanium (Ge); X is oxygen (O), sulfur (S),nitrogen (N) or a lone pair of electrons; n is 1 or 2; R¹, R^(1′), R²and R^(2′) are each independently H, C-4 to C-50 alkyl, C-6 to C-50aryl, silyl, C-4 to C-50 substituted arylalkyl, C-6 to C-50 substitutedalkylaryl, alkoxy, dialkylamino, or alkylhio; R³, R3′, R⁴ and R^(4′) areeach independently C-1 to C-20 alkyl, or C-1 to C-20 fluoroalkyl.Typically, R1, R1′, R2 and R2′ are tert-butyl or phenyl. When X issubstituted N, the substituents can be C-1 to C-10 alkyl or aryl,including ═N—N═N-Ad, where Ad represents an adamantyl group:

While the formula above shows the phosphorus-containing ligands arrangedaround E in a “trans” formation, they can also be arranged around E in a“cis” formation. Because the substituents can be different, thecompounds can be symmetric and non-symmetric in nature.

A general scheme, below, shows the reaction of the (^(t)Bu)₂PCH₂(CF₃)₂OHwith bis[bis(trimethylsilyl)amino]tin(II) (structure 1 below) to givetin(II), trans-bis[3-(di-tert-butylphosphino)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanolato-O,P]—(structure 2 below). The reaction generally takes place in the presenceof a solvent, typically toluene, and the final product is generallyrecrystallized in the presence of a solvent, generally non-polar C-4 toC-20 hydrocarbon solvents, typically pentene, before X-raycrystallographic analysis.

The resulting divalent tin compound 2 can subsequently be reacted withsulfur to form the compound 3, tin(II),trans-bis[3-(di-tert-butylphosphinothioyl)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanolato-κO,κS]—, shown in the scheme below. This reaction is demonstrated inExample 2 below.

Other reactions of the divalent tin compound 2 have been demonstrated.1-Azidoadamantane reacts with compound 2 also on the phosphorus centers.Only mono-adduct 4 was formed in this reaction. Addition of the secondmolecule of 1-azidoadamantane did not take place even upon heating thereaction mixture at 100° C. for 2 weeks. Therefore, non-symmetricalstructures can be obtained.

In likewise fashion, sterically bulky phosphine compounds can be used tosynthesize germanium complexes. The reaction between lithium salt of2-[(di-tert-butyl-phosphanyl)methyl]-1,1,1,3,3,3-hexafluoropropan-2-ol 5(obtained by reacting di-tert-butyl phosphine with butyl lithium, andsubsequent reaction with 2,2-bis-trifluoromethyl-oxirane) andgermanium(II) chloride dioxane complex was used to prepare the divalentgermanium compound 6 supported by two P^O chelating five-membered rings,as shown in the scheme below. As used herein, P^O represents a series ofatoms and bonds, with P on one end and O on the other, where otheratom(s) may or may not be present between. P^O therefore represents theatoms that are important for coordination as it identifies thecoordination points (P and O).

As described in the examples below, in general, when E is Sn in formulaA above, the compound can be made by adding a generally an alkyl alcoholto a dialkyl tin compound of the general formula Sn(—N(R²))₂, where R isC-1 to C-20 alkyl, compound to give (RO)₂Sn material. Also, in general,when E is Ge in formula A above, the compound can be made by addinggenerally a C1-C20 alkyl Lithium oxide (R-OLi) to a substituted orunsubstituted Germanium chloride (GeCl₂) to give (RO)₂Ge material.

The process reactions described herein can take place at any convenienttemperature, generally between 0 degrees C. and 120 degrees C., andpreferably between 60 degrees C. and 80 degrees C. Any convenientpressure can be used, with ambient pressure preferred.

The production of polyurethane is usually achieved by addition ofpolymeric polyols to isocyanates. Polyols are generally defined aspolymeric or oligomeric organic species with at least two hydroxyfunctionalities. A schematic of a polyol used herein is shown below asstructure 7. Unless otherwise stated, the term “polyol”, when usedherein with regard to processes for making polyurethanes, refers to thepolyol having structure 7. The polyol is available from DuPont,Wilmington, Del.

The starting Polyol may be either a low molecular weight oligomer(generally from about 500 to 3000 wt. avg. molecular weight, preferablyfrom about 600 to about 2000 wt. avg. molecular weight) or a polymerwith OH functionality (generally from about 2000 to about 300,000 wt.avg. molecular weight, preferably from about 2500 to about 100,000 wt.avg. molecular weight, and more preferably from about 2500 to about50,000 wt. avg. molecular weight.

The production of a polyurethane may also use other isocyanate-reactivecompounds, including but not limited to alcohols, amines, thiols andcombinations thereof.

An example of the isocyanate with functional groups capable of reactingwith hydroxyl is as follows:

wherein R₅ is a alkyl structure, such as, for example, ethyl, propyl,phenyl and the like. In some preferred embodiments, R₅ is (CH₂)₆.

Examples of isocyanates suitable for use in producing polyurethanesinclude aromatic, aliphatic or cycloaliphatic di-, tri- ortetra-isocyanates, including polyisocyanates having isocyanuratestructural units, such as, the isocyanurate of hexamethylenediisocyanate and isocyanurate of isophorone diisocyanate; the adduct of2 molecules of a diisocyanate, such as, hexamethylene diisocyanate and adiol such as, ethylene glycol; uretidiones of hexamethylenediisocyanate; uretidiones of isophorone diisocyanate or isophoronediisocyanate; the adduct of trimethylol propane andmeta-tetramethylxylene diisocyanate.

Additional examples of suitable polyisocyanates include 1,2-propylenediisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate,2,3-butylene diisocyanate, hexamethylene diisocyanate, octamethylenediisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate,2,4,4-trimethyl hexamethylene diisocyanate, dodecamethylenediisocyanate, omega, omega-dipropyl ether diisocyanate, 1,3-cyclopentanediisocyanate, 1,2-cyclohexane diisocyanate, 1,4-cyclohexanediisocyanate, isophorone diisocyanate,4-methyl-1,3-diisocyanatocyclohexane, trans-vinylidene diisocyanate,dicyclohexylmethane-4,4′-diisocyanate,3,3′-dimethyl-dicyclohexylmethane-4,4′-diisocyanate, a toluenediisocyanate, 1,3-bis(1-isocyanatol-methylethyl)benzene,1,4-bis(1-isocyanato-1-methylethyl)benzene,1,3-bis(isocyanatomethyl)benzene, xylene diisocyanate,1,5-dimethyl-2,4-bis(isocyanatomethyl)benzene,1,5-dimethyl-2,4-bis(2-isocyanatoethyl)benzene,1,3,5-triethyl-2,4-bis(isocyanatomethyl)benzene,4,4′-diisocyanatodiphenyl, 3,3′-dichloro-4,4′-diisocyanatodiphenyl,3,3′-diphenyl-4,4′-diisocyanatodiphenyl,3,3′-dimethoxy-4,4′-diisocyanatodiphenyl,4,4′-diisocyanatodiphenylmethane,3,3′-dimethyl-4,4′-diisocyanatodiphenyl methane, adiisocyanatonaphthalene, polyisocyanates having isocyanaurate structuralunits, the adduct of 2 molecules of a diisocyanate, such as,hexamethylene diisocyanate or isophorone diisocyanate, and a diol suchas ethylene glycol, the adduct of 3 molecules of hexamethylenediisocyanate and 1 molecule of water (available under the trademarkDesmodur® N from Bayer Corporation of Pittsburgh, Pa.), the adduct of 1molecule of trimethylol propane and 3 molecules of toluene diisocyanate(available under the trademark Desmodur® L from Bayer Corporation), theadduct of 1 molecule of trimethylol propane and 3 molecules ofisophorone diisocyanate, compounds such as 1,3,5-triisocyanato benzeneand 2,4,6-triisocyanatotoluene, and the adduct of 1 molecule ofpentaerythritol and 4 molecules of toluene diisocyanate. Otherisocyanate-comprising materials can be used, including but not limitedto thioisocyanates, selenium isocyanates, carbodiimides (R—N═C═N—R) andthe like

A specific example of an isocyanate capable of reacting with hydroxylgroups is Desmodur® 3300 isocyanate, available from Bayer. Desmodur®3300 as available commercially, comprises a mixture of compounds, with ageneral structure as follows (also, pentamer, heptamer and highermolecular weight species can be present):

It is preferred that the compositions made before reaction with thecatalyst be of relatively low molecular weight (generally less thanabout 50,000 wt. avg. molecular weight so as to keep the viscosity ofthe compositions before crosslinking low, and therefore avoid orminimize the need for solvent(s).

Other materials, which may be present in the compositions and processes,include one or more solvents (and are meant to act only as solvents).These preferably do not contain groups such as hydroxyl or primary orsecondary amino.

The tin and geranium compounds as prepared herein were tested ascatalysts for polyurethane formation. Two important parameters wererecorded: gel time under anaerobic conditions (under nitrogen) and geltime under aerobic conditions. The so-called “gel time” corresponded tothe time in hours following activation at which flow is no longerobserved in a coating mixture. The “gel time” demonstrates “latency”,wherein the materials formed would still be sprayable as coatings, andwould be attractive for the refinish automotive market. The results ofthe application of novel divalent tin and germanium compounds in thecatalytic formation of polyurethanes are shown in the Table in theExamples below. Generally, when the catalysts of some of the embodimentsof the present invention are used to produce polyurethanes, gel timesincrease from 2 to 50 times under nitrogen, and 3 to 40 times underaerobic (air) conditions, compared to those of polyurethanes madewithout catalysts expressed in some of the embodiments of the presentinvention.

Crosslinked polyurethanes prepared according to the processes disclosedherein are useful, for example, as encapsulants, sealants, and coatings,especially transportation (automotive) and industrial coatings. Astransportation coatings, the present compositions are useful as both OEM(original equipment manufacturer) and automotive refinish coatings. Theymay also be used as primer coatings. They often cure under ambientconditions to tough hard coatings and may be used as one or both of theso-called base coat and clear coat automotive coatings. This makes themparticularly useful for repainting of transportation vehicles in thefield.

Depending on use, the compositions and the materials used in the presentprocesses may contain other materials. For example, when used asencapsulants and sealants, the compositions may contain fillers,pigments, and/or antioxidants.

When used as coatings, the present compositions contain typically addedingredients known in the art, which are described below. In particularthere may be other polymers (especially of low molecular weight,“functionalized oligomers”) which are either inert or have functionalgroup other than hydroxyl or isocyanate and also react with otherreactive materials in the coating composition.

Representative of the functionalized oligomers that can be employed ascomponents or potential crosslinking agents of the coatings are thefollowing:

Hydroxyl oligomers: The reaction product of multifunctional alcoholssuch as pentaerythritol, hexanediol, trimethylol propane, and the like,with cyclic monomeric anhydrides such as hexahydrophthalic anhydride,methylhexahydrophthalic anhydride, and the like produce acid oligomers.These acid oligomers are further reacted with monofunctional epoxiessuch as butylene oxide, propylene oxide, and the like to form hydroxyloligomers.

Silane oligomers: The above hydroxyl oligomers further reacted withisocyanato propyltrimethoxy silane.

Epoxy oligomers: The diglycidyl ester of cyclohexane dicarboxylic acid,such as Araldite® CY—184 from Ciba Geigy, and cycloaliphatic epoxies,such as ERL®—4221, and the like from Union Carbide.

Aldimine oligomers: The reaction product of isobutyraldehyde withdiamines such as isophorone diamine, and the like.

Ketimine oligomers: The reaction product of methyl isobutyl ketone withdiamines such as isophorone diamine.

Melamine oligomers: Commercially available melamines such as CYMEL® 1168from Cytec Industries, and the like.

AB-Functionalized oligomers: Acid/hydroxyl functional oligomers made byfurther reacting the above acid oligomers with 50%, based onequivalents, of monofunctional epoxy such as butylene oxide or blends ofthe hydroxyl and acid oligomers mentioned above or any other blenddepicted above.

CD-Functionalized Crosslinkers: Epoxy/hydroxyl functional crosslinkerssuch as the polyglycidyl ether of Sorbitol DCE—358® from Dixie Chemicalor blends of the hydroxyl oligomers and epoxy crosslinkers mentionedabove or any other blend as depicted above.

The compositions of this invention may additionally contain a binder ofa noncyclic oligomer, i.e., one that is linear or aromatic. Suchnoncyclic oligomers can include, for instance, succinic anhydride- orphthalic anhydride-derived moieties in hydroxyl oligomers.

Preferred functionalized oligomers have weight average molecular weightnot exceeding about 3,000 with a polydispersity not exceeding about 1.5;more preferred oligomers have molecular weight not exceeding about 2,500and polydispersity not exceeding about 1.4; most preferred oligomershave molecular weight not exceeding about 2,200, and polydispersity notexceeding about 1.25. Other additives also include polyaspartic esters,which are the reaction product of diamines, such as, isopherone diaminewith dialkyl maleates, such as, diethyl maleate.

The coating compositions may be formulated into high solids coatingsystems dissolved in at least one solvent. The solvent is usuallyorganic. Preferred solvents include aromatic hydrocarbons such aspetroleum naphtha or xylenes; ketones such as methyl amyl ketone, methylisobutyl ketone, methyl ethyl ketone or acetone; esters such as butylacetate or hexyl acetate; and glycol ether esters such as propyleneglycol monomethyl ether acetate.

The coating compositions can also contain a binder of an acrylic polymerof weight average molecular weight greater than 3,000, or a conventionalpolyester such as SCD®—1040 from Etna Product Inc. for improvedappearance, sag resistance, flow and leveling and such. The acrylicpolymer can be composed of typical monomers such as acrylates,methacrylates, styrene and the like and functional monomers such ashydroxy ethyl acrylate, glycidyl methacrylate, or gammamethacrylylpropyl trimethoxysilane and the like.

The coating compositions can also contain a binder of a dispersedacrylic component which is a polymer particle dispersed in an organicmedia, which particle is stabilized by what is known as stericstabilization. Hereafter, the dispersed phase or particle, sheathed by asteric barrier, will be referred to as the “macromolecular polymer” or“core”. The stabilizer forming the steric barrier, attached to thiscore, will be referred to as the “macromonomer chains” or “arms”.

The dispersed polymer contains about 10 to 90%, preferably 50 to 80%, byweight, based on the weight of the dispersed polymer, of a highmolecular weight core having a weight average molecular weight of about50,000 to 500,000. The preferred average particle size is 0.1 to 0.5microns. The arms, attached to the core, make up about 10 to 90%,preferably 10 to 59%, by weight of the dispersed polymer, and have aweight average molecular weight of about 1,000 to 30,000, preferably1,000 to 10,000. The macromolecular core of the dispersed polymer iscomprised of polymerized acrylic monomer(s) optionally copolymerizedwith ethylenically unsaturated monomer(s). Suitable monomers includestyrene, alkyl acrylate or methacrylate, ethylenically unsaturatedmonocarboxylic acid, and/or silane-containing monomers. Such monomers asmethyl methacrylate contribute to a high Tg (glass transitiontemperature) dispersed polymer, whereas such “softening” monomers asbutyl acrylate or 2-ethylhexylacrylate contribute to a low Tg dispersedpolymer. Other optional monomers are hydroxyalkyl acrylates ormethacrylates or acrylonitrile. Optionally, the macromolecular core canbe crosslinked through the use of diacrylates or dimethacrylates such asallyl methacrylate or post reaction of hydroxyl moieties withpolyfunctional isocyanates. The macromonomer arms attached to the corecan contain polymerized monomers of alkyl methacrylate, alkyl acrylate,each having 1 to 12 carbon atoms in the alkyl group, as well as glycidylacrylate or glycidyl methacrylate or ethylenically unsaturatedmonocarboxylic acid for anchoring and/or crosslinking. Typically usefulhydroxy-containing monomers are hydroxy alkyl acrylates or methacrylatesas described above.

The coating compositions can also contain conventional additives such aspigments, stabilizers, rheology control agents, flow agents, tougheningagents and fillers. Such additional additives will, of course, depend onthe intended use of the coating composition. Fillers, pigments, andother additives that would adversely affect the clarity of the curedcoating may not typically be included if the composition is intended asa clear coating.

The coating compositions are typically applied to a substrate byconventional techniques such as spraying, electrostatic spraying, rollercoating, dipping or brushing. The present formulations are particularlyuseful as a clear coating for outdoor articles, such as automobile andother vehicle body parts. The substrate is generally prepared with aprimer and or a color coat or other surface preparation prior to coatingwith the present compositions.

A layer of a coating composition is cured under ambient conditions inthe range of 30 minutes to 24 hours, preferably in the range of 30minutes to 3 hours to form a coating on the substrate having the desiredcoating properties. One of skill in the art appreciates that the actualcuring time depends upon the thickness of the applied layer and on anyadditional mechanical aids, such as, fans that assist in continuouslyflowing air over the coated substrate to accelerate the cure rate. Ifdesired, the cure rate may be further accelerated by baking the coatedsubstrate at temperatures generally in the range of from about 60° C. to150° C. for a period of about 15 to 90 minutes. The foregoing bakingstep is particularly useful under OEM (Original Equipment Manufacture)conditions.

The compounds and processes disclosed herein can be used for makingcoating compositions and generally in applications wherein curing ofpolyurethane is required, for example in the adhesives industry andrelated applications. The compositions are also suitable as clear orpigmented coatings in industrial and maintenance coating applications.

A coating composition made using the catalysts is suitable for providingcoatings on variety of substrates, particularly for providing clearcoatings in automotive OEM or refinish applications typically used incoating auto bodies. The coating composition can be formulated in theform of a clear coating composition, pigmented composition, metallizedcoating composition, basecoat composition, monocoat composition or aprimer. The substrate is generally prepared with a primer and or a colorcoat or other surface preparation prior to coating with the presentcompositions.

Suitable substrates to which the coating compositions can be appliedinclude automobile bodies, items manufactured and painted by automobilesub-suppliers, frame rails, commercial trucks and truck bodies,including but not limited to beverage bodies, utility bodies, ready mixconcrete delivery vehicle bodies, waste hauling vehicle bodies, and fireand emergency vehicle bodies, as well as potential attachments orcomponents to such truck bodies, buses, farm and construction equipment,truck caps and covers, commercial trailers, consumer trailers,recreational vehicles, including but not limited to, motor homes,campers, conversion vans, vans, pleasure vehicles, pleasure craft snowmobiles, all terrain vehicles, personal watercraft, motorcycles,bicycles, boats, and aircraft. Other suitable substrates for coatinginclude industrial and commercial new construction and maintenancethereof; cement and wood floors; walls of commercial and residentialstructures, such office buildings and homes; amusement park equipment;concrete surfaces, such as parking lots and drive ways; asphalt andconcrete road surface, wood substrates, marine surfaces; outdoorstructures, such as bridges, towers; coil coating; railroad cars;printed circuit boards; machinery; OEM tools; signage; fiberglassstructures; sporting goods; golf balls; and sporting equipment.

EXAMPLES

All air-sensitive compounds were prepared and handled under a N₂/Aratmosphere using standard Schlenk and inert-atmosphere box techniques.Anhydrous solvents were used in the reactions. Solvents were distilledfrom drying agents or passed through columns under an argon or nitrogenatmosphere. 1-Azidoadamantane, sulfur,bis[bis(trimethylsilyl)amino]tin(II), germanium(II) chloride dioxanecomplex (1:1), and n-butanol were purchased from Aldrich Chemical Co.,Milwaukee, Wis. Unless otherwise specified, all other chemicals andreagents were also obtained from Aldrich Chemical Co.

As used in the following examples, “Polyol” means a compound having thestructure 7 shown above. Unless otherwise stated, the polyol was used as50% solids dissolved in methyl amyl ketone, butyl acetate, and propyleneglycol methyl ether acetate.

The isocyanate species used in the examples below was Desmodur® 3300A,an oligomer of hexamethylene diisocyanate which is commerciallyavailable from Bayer Incorporated, 100 Bayer Road, Pittsburgh, Pa.15205-9741.

Example 1 Tin(II),trans-bis[3-(di-tert-butylphosphino)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanolato-O,P]—

15.62 g (0.048 mol) of2-[(Di-tert-butyl-phosphanyl)methyl]-1,1,1,3,3,3-hexafluoropropan-2-olwas dissolved in 200 ml of toluene. 9.5 g (0.022 mol) ofBis[bis(trimethylsilyl)amino]tin(II) was added dropwise in abovesolution. The reaction mixture was stirred for 24 hours and the solventand formed bis(trimethylsilyl)amine were removed in 1-mm vacuum. Theresidue was recrystallized from 50 ml of pentane at −30° C. Yield oftin(II),trans-bis[3-(di-tert-butylphosphino)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanolato-O,P]—,was 12.71 g (76%) as a white solid with m.p. 207.6° C. (decomposition).¹H NMR (500 MHz, C₆D₆, TMS): δ 1.00 (s, 36H, Me), 2.10 (s, 4H, CH₂). ¹⁹FNMR (500 MHz, Tol-D₈): δ−76.85 (s, 12F). ³¹P NMR (500 MHz, Tol-D₈): δ18.2 (¹J_(P119Sn)=865.36 Hz, ¹J_(P117Sn)=827.18 Hz). ¹¹⁹Sn NMR (400 MHz,C₆D₆, Me₄Sn): δ−292.0 (br, 1Sn). Anal. Calculated for C₂₄H₄₀F₁₂O₂P₂Sn(Mol. Wt.: 769.21): C, 37.47; H, 5.24. Found: C, 37.54; H, 5.27. Thestructure was proven by X-ray analysis.

Example 2 Tin(II),trans-bis[3-(di-tert-butylphosphinothioyl)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanolato-κO,κS]—

3.0 g (0.0039 mol) of Tin(II),trans-bis[3-(di-tert-butylphosphino)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanolato-O,P]—(example 1) and 0.27 g (0.0086 mol) of sulfur were stirred in 200 ml oftoluene at room temperature for 48 hours. The solvent was removed in1-mm vacuum and the residue was recrystallized from 50 ml of pentane.Yield of tin(II),trans-bis[3-(di-tert-butylphosphinothioyl)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanolato-κO,κS]—,was 3.14 g (97%) as a white solid with m.p. 204.5° C. (decomposition).¹H NMR (500 MHz, C₆D₆, TMS): δ 1.00 (s, 36H, Me), 2.30 (s, 4H, CH₂). ¹⁹FNMR (500 MHz, C₆D₆): δ−76.30 (s, 12F). ³¹P NMR (500 MHz, THF-D₈): δ67.11 (²J_(P119Sn)=114.4 Hz). ¹⁹Sn NMR (400 MHz, THF-D₈, Me₄Sn): δ−489.3(br, 1Sn). Anal. Calculated for C₂₄H₄₀F₁₂O₂P₂S₂Sn (Mol. Wt.: 833.34): C,34.59; H, 4.84. Found: C, 34.72; H, 5.03. The structure was proven byX-ray analysis.

Example 32-(Di-tert-butyl-phosphinoylmethyl)-1,1,1,3,3,3-hexafluoro-propan-2-ol

1.0 g (0.0013 mol) of Tin(II),trans-bis[3-(di-tert-butylphosphino)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanolato-O,P]—,(example 1) was dissolved in 50 ml of methylene chloride, then 1.0 g ofthe 30% solution of hydrogen peroxide was added in the above solution.After 1 hour, the organic phase was separated, dried over magnesiumsulfate over night.

The solvent was removed in 1-mm vacuum and the residue wasrecrystallized from 10 ml of pentane. Yield of2-(di-tert-butyl-phosphinoylmethyl)-1,1,1,3,3,3-hexafluoro-propan-2-ol]-,was 0.71 g (80%) as a white solid with m.p. 87.5° C. (with sublimation).¹H NMR (500 MHz, THF-D₈, TMS): δ 1.12 (d, ³J_(P,H)=13.4 Hz, 18H, Me),2.30 (d, ³J_(P,H)=3.7 Hz, 2H, CH₂). ¹⁹F NMR (500 MHz, THF-D₈): δ−81.20(s, 12F). ³¹P NMR (500 MHz, THF-D₈): δ 64.95 (s, 1P). Anal. Calculatedfor C₁₂H₂₁F₆O₂P (Mol. Wt.: 342.26): C, 42.11; H, 6.18; P, 9.05. Found:C, 42.25; H, 6.22; P, 9.13. The structure was proven by X-ray analysis.

Example 4 Synthesis of Tin(II),trans-[3-(di-tert-butylphosphino)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanolato-O,P],[3-(di-tert-butyl-(phosphinyl)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanolato-κO,κN]— and Tin(II),trans-bis[3-(di-tert-butylphosphinoyl)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanolato-κO,κS]-.

3.0 g (0.0039 mol) of Tin(II),trans-bis[3-(di-tert-butylphosphino)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanolato-O,P]—,(example 1) and 4.05 g (0.043 mol) of pyridine-N-oxide were stirred in200 ml of toluene at 100° C. for 5 weeks. According to ³¹P NMR 20% ofthe starting compound was consumed to give two new signals in about 2 to1 ratio. Tin(II),trans-[3-(di-tert-butylphosphino)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanolato-O,P],[3-(di-tert-butyl-(phosphinyl)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanolato-κO,κN]—, has following chemical shifts ³¹P NMR (500 MHz, THF-D₈): δ 64.8(d, ³J_(PP)=18.7 Hz, ²J_(P119Sn)=118.9 Hz, 1P, P═O), 19.9 (d,³J_(PP)=18.7 Hz, ¹J_(P119Sn)=270.8 Hz, 1P). Tin(II),trans-bis[3-(di-tert-butylphosphinoyl)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanolato-κO,κS]—, has following chemical shifts ³¹P NMR (500 MHz, THF-D₈): δ 60.7(²J_(P119Sn)=96.33 Hz).

Example 5 Tin(II),trans-[3-(di-tert-butylphosphino)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanolato-O,P],[3-(P,P-di-tert-butyl-N-(diazo-adamantyl)phosphinimyl)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanolato-κO,κN]—,

3.0 g (0.0039 mol) of Tin(II),trans-bis[3-(di-tert-butylphosphino)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanolato-O,P]—,(example 1) and 0.63 g (0.0041 mol) of 1-azidoadamantane were stirred in200 ml of toluene at room temperature for 5 days. The solvent wasremoved in 1-mm vacuum and the residue was recrystallized from 50 ml ofpentane. Yield of tin(II),trans-[3-(di-tert-butylphosphino)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanolato-O,P],[3-(P,P-di-tert-butyl-N-(diazo-adamantyl)phosphinimyl)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanolato-κO,κN]—, was 3.20 g (87%) as a slight yellow solid with m.p. 167.7° C.(decomposition). In the structure above, Ad represents an adamantylgroup. ¹H NMR (500 MHz, C₆D₆, TMS): δ 1.05 (d, ³J_(P,H)=13.8 Hz, 9H,Me), 1.16 (d, ³J_(P,H)=13.8 Hz, 9H, Me), 1.20 (d, ³J_(P,H)=14.7 Hz, 9H,Me), 1.35 (d, ³J_(P,H)=14.4 Hz, 9H, Me), 1.63 (m, 6H, Adamantyl), 1.90(m, 6H, Adamantyl), 2.05 (m, 3H, Adamantyl), 2.40 (m, 2H, P—CH₂), 2.30(m, 2H, P—CH₂). ¹⁹F NMR (500 MHz, C₆D₆): δ−74.55 (m, 3F), −74.87 (m,3F), −76.24 (m, 3F), −77.82 (m, 3F). ³¹P NMR (500 MHz, Tol-D₈): δ 12.50(d, ²J_(PP)=12.90 Hz, ¹J_(P119Sn)=414.19 Hz, 1P), 59.60 (d,²J_(PP)=12.90 Hz, ²J_(P119Sn)=103.79 Hz, 1P). ¹⁹Sn NMR (400 MHz, THF-D₈,Me₄Sn): δ−488.2 (br, 1Sn). Anal. Calculated for C₃₄H₅₅F₁₂N₃O₂P₂Sn (Mol.Wt.: 946.47): C, 43.15; H, 5.86; N, 4.44. Found: C, 43.26; H, 6.01; N,4.63. The structure was proven by X-ray analysis.

Example 6 Germanium(II),trans-bis[3-(di-tert-butylphosphino)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanolato-O,P]—,

14.45 g (0.095 mol) of Lithium di-tert-butylphosphine, 18.81 g (0.105mol) of 2,2-bis(trifluoromethyl)oxirane and 80 ml of THF were stirred atroom temperature for 1 hour. Then 10.0 g (0.043 mol) of germanium(II)chloride dioxane complex (1:1) was added by one portion to the reactionmixture. The reaction mixture was stirred for 24 hours and the solventwas removed in 1-mm vacuum. The residue was redissolved in 100 ml ofpentane. The LiCl was filtered off and the final product was purified bythe recrystallization from 50 ml of pentane at −30° C. Yield of isgermanium(II),trans-bis[3-(di-tert-butylphosphino)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanolato-O,P]—,was 14.3 g (46%) as a white solid with m.p. 186.2° C. (decomposition).¹H NMR (500 MHz, THF-D₈, TMS): δ 1.30 (s, 36H, Me), 2.35 (s, 4H, CH₂).¹⁹F NMR (500 MHz, THF-D₈): 6-76.58 (s, 12F). ³¹P NMR (500 MHz, THF-D₈):δ 15.2 (s, 1P). Anal. Calculated for C₂₄H₄₀F₁₂O₂GeP₂ (Mol. Wt.: 723.14):C, 39.86; H, 5.58. Found: C, 40.03; H, 6.17. The structure was proven byX-ray analysis.

Example 7 Reaction of 1-azidoadamantane with germanium(II),trans-bis[3-(di-tert-butylphosphino)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanolato-O,P]—, toproduce Germanium(IV),trans-[3-(tert-butylphosphino)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanolato-κO,κP],[3-(P,P-di-tert-butyl-phosphinimyl)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanolato-κO,κN]—,

3.0 g (0.0042 mol) of Germanium(II),trans-bis[3-(di-tert-butylphosphino)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanolato-O,P]—,(example 6) and 1.6 g (0.0090 mol) of 1-azidoadamantane were stirred in600 ml of toluene at 100° C. for 5 days. The solvent was removed in 1-mmvacuum and the residue was recrystallized from 50 ml of pentane. Thefirst crop of the crystals was germanium(IV),trans-[3-(tert-butylphosphino)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanolato-κO,κP],[3-(P,P-di-tert-butyl-phosphinimyl)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanolato-κO,κN]—. Yield of the compound was 1.10 g (39%) as a white solid with m.p.83.7° C. (decomposition). ¹H NMR (500 MHz, C₆D₆, TMS): δ 1.20 (d,³J_(P,H)=13.7 Hz, 9H, Me), 1.25 (d, ³J_(P,H)=13.6 Hz, 9H, Me), 1.29 (d,³J_(P,H)=14.0 Hz, 9H, Me), 1.34 (d, ³J_(P,H)=14.1 Hz, 9H, Me), 2.40 (m,2H, P—CH₂), 2.70 (m, 2H, P—CH₂). ¹⁹F NMR (500 MHz, C₆D₆): δ−77.25 (m,3F), −80.57 (m, 3F), −81.00 (m, 3F), −82.93 (m, 3F). ³¹P NMR (500 MHz,THF-D₈): δ−69.99 (s, 1P), 42.27 (s, 1P). Anal. Calculated forC₂₀H₃₁F₁₂GeNO₂P₂ (Mol. Wt.: 680.03): C, 35.32; H, 4.59; N, 2.06. Found:C, 35.37; H, 4.73; N, 2.30. The structure was proven by X-ray analysis.The second crop wasoxo-bis[adamantyl[3-(P,P-di-tert-butyl-phosphinimyl)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanolato-κO,κN] germanium(IV)]. Yield of the second compound 17 was 0.37 g (16%) asa white solid with m.p. 104.8° C. (decomposition). ¹H NMR (500 MHz,THF-D₈, TMS): δ 1.15 (d, ³J_(P,H)=13.7 Hz, 18H, Me), 1.30 (d,³J_(P,H)=13.8 Hz, 18H, Me), 1.68 (m, 12H, Adamantyl), 1.91 (m, 12H,Adamantyl), 2.10 (m, 6H, Adamantyl), 2.20 (m, 4H, P—CH₂). ¹⁹F NMR (500MHz, THF-D₈): δ−79.80 (m, 3F), −80.60 (m, 3F). ³¹P NMR (500 MHz,THF-D₈): δ 39.02 (s, 2P). Anal. Calculated for C₄₄H₇₀F₁₂Ge₂N₂O₃P₂ (Mol.Wt.: 1110.25): C, 47.60; H, 6.35; N, 2.52. Found: 47.64; H, 6.41; N,2.58. The structure was proven by X-ray analysis. The residue from therecrystallizations was subjected to the chromatography on silica gelwith the eluent petroleum ether/ethyl ether at 10/0.5.2-[(P,P-Di-tert-butyl-N-adamantylphosphinimyl)methyl]-1,1,1,3,3,3-hexafluoropropan-2-olwas formed.

Yield of this compound was 1.03 g (26%) as a white solid with m.p.82.43° C. (decomposition). ¹H NMR (500 MHz, C₆D₆, TMS): δ 0.85 (d,³J_(P,H)=12.8 Hz, 9H, Me), 0.94 (d, ³J_(P,H)=12.9 Hz, 9H, Me), 1.50 (m,6H, Adamantyl), 1.70 (m, 6H, Adamantyl), 1.90 (m, 3H, Adamantyl), 2.20(m, 2H, P—CH₂). ¹⁹F NMR (500 MHz, C₆D₆): δ−78.07 (m, 3F), −78.41 (m,3F). ³¹P NMR (500 MHz, C₆D₆): δ 84.33 (s, 1P). Anal. Calculated forC₂₂H₃₆F₆NOP (Mol. Wt.: 475.49): C, 55.57; H, 7.63; N, 2.95. Found: C,55.74; H, 7.69; N, 3.12. The structure was proven by X-ray analysis.

Polymerization Procedure

All test samples were prepared under a nitrogen atmosphere. The stocksolutions were prepared so that the test concentrations were at amaximum of 10% of the concentration of the stock solution, i.e. 8% stocksolution for the pre-catalyst to test at 7700 ppm. Samples were preparedby taking a known mass of the pre-catalyst and diluting it with butylacetate until it reached a total mass for that of the desired percent.The starting materials for the gel time were measured out with 1.95 g ofDesmodur®3300 and 4.74 g of Polyol. To this mixture was added thecalculated amount of stock solution to produce the desired concentrationof the pre-catalyst and the contents mixed. From this two samples areproduced; one was left stirring under a nitrogen atmosphere and theother was left stirring exposed to air. The samples were checkedfrequently and time it took for the samples to gel was recorded forboth. The results shown in the table below.

TABLE Gel times under nitrogen and under air for compounds in theformation of polyurethanes. Time to Concen- gel under Time to trationnitrogen gel under Entry Compound (ppm) (hrs) air (hrs) 1 Ex. 1 1500 1.61.93 2 Ex. 1 700 2.6 2.27 3 Ex. 1 500 3.23 3.07 4 Ex. 1 250 6.23 5.73 5Ex. 2 1800 1.46 0.96 6 Ex. 2 1000 2.63 1.96 7 Ex. 5 5000 11.0 11.0 8 Ex.5 500 19.0 19.0 9 Ex. 6 4000 38.0 7.9 10 (^(t)Bu₂P—CH₂—C(CF₃)₂OH 180072.0 72.0 11 No catalyst N/A 72.0 72.0

1. A compound having formula:

wherein E is tin (Sn) or germanium (Ge); X is oxygen, sulfur, nitrogen,substituted N, or a lone pair of electrons; n is 2; R¹ and R² are eachindependently H, C-4 to C-50 alkyl, C-6 to C-50 aryl, silyl, C-4 to C-50substituted arylalkyl, C-6 to C-50 substituted alkylaryl, alkoxy,dialkylamino, or alkylhio; and R³ and R⁴ are each independently C-1 toC-20 alkyl, or C-1 to C-20 fluoroalkyl.
 2. The compound of claim 1,wherein E is Sn, R¹ and R² are each tert-butyl, R³ and R⁴ are each CF₃.3. The compound of claim 1, wherein E is Ge, R¹ and R² are eachtert-butyl, R³ and R⁴ are each CF₃.